Supported catalysts and process for preparation thereof



rm... a. 9, 1945 UNITED I STATES PATENT OFFlCE SUPPORTED CATALYSTS AND PROCESS FOR PREPARATION THEREOF John D. Upham, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing Application March 4, 1943,

- Serial No.'478,028

Claims. .(Cl. 252-210) This invention relates to the preparation and utilization of catalysts, more particularly, supported catalysts which have one or more metal .oxides or metals as active constituents.

Catalysts comprising one or more metal oxides or metals supported on suitable .carrier materials.

the supporting material in the form of an aqueous solution of a salt which upon being heated decomposes to the desired metal oxide. In another conventional method, the active'ingredient is added to the support in the form of an aqueous solution and is then precipitated on orin the supporting material with an aqueous solution of an alkali, and the resulting supported hydrous oxide or hydroxide is dried. In the final precipitation, according to this method, an exceedingly voluminous precipitate 'of hydrous oxide may form in such quantities that some of it may ooze or creep from the pores of the support and, on drying, form a loose powder or fines disassociated or inadequately associated with the support. Furthermore, the formation of such a v'oluminoushydrous oxide may exert such a strong pressure within the support granules that a considerable fraction of these granules are split or broken apart, forming fines from the support itself. As a consequence, a substantial amount of catalytic material may be lost thereby. The finished catalyst, if it contains substantial amount of fines, may produce undesirable packing and/or channeling in converters in which itis used. Fines are especially undesirable with supports that consist of manufactured pellets of uniform size and shape. During the precipitation aqueous alkaline solutions may not penetrate suill cien=tly into the pores of the support to precipitate completely all the metal salt in the form of hydroxide or hydrous oxide according to conventional methods, and frequently detrimental amounts of so-called acid residues are engendered. I

An object of this invention is to provide superior supported metal oxide or metal catalysts of high activity and long life and improved methods for their production.

A specific object of this invention is to provide a process for the preparation of supported catalysts which avoids'substantial disruption of support granules that may occur when precipitation of metal hydroxides or hydrous oxides on or in a porous carrier is practiced in the conventional manner.

Another specific object isto provide a'process for the preparation of a supported catalyst having granules of uniform size and shape, predetermined by the size and shape of the granules of the supporting material, without the necessity for briquetting or pelleting subsequent to impregnation of the supporting material with the active ingredient.

Another specific object is to provide a process for the preparation of supported catalysts that contain more catalytic metal oxide material withinthe pores of the carrier or support than that obtained when the oxide material is formed in the conventional way.

Another specific object is to provide improved processes for the catalytic treatment and/or conversion of hydrocarbons.

" Other objects and advantages of this invention, some of which are referred to specifically hereinafter, will be apparent from the following description and the appended claims.

In accordance with one specific. embodiment of this invention, supported metal oxide catalysts of high activity and long life are advantageously prepared by impregnating a suitable difficultly fusible or refractory porous granular carrier or support with a solution of at least one polyvalent metal salt of a monobasic acid. The formation or precipitation of the desired metal oxide is completed in or on the carrier by a treatment with substantially anhydrous, gaseous or liquid ammonia. The carrier impregnated with solution may be dried, partially or completely, prior to treating it with anhydrous ammonia. Subsequent to precipitation with anhydrous ammonia, 1 the catalyst may be agitated for a short time with a dilute alkaline, solution, for example, 2 per cent potassium hydroxide, as described in the copending application oi; David G.-Blaker,' Serial No.

365,369, filed November 12, 1940, to remove or.

counteract undesirable acid residue.

In general, my invention is applicable to any supported metal oxide catalyst in. which one or more of the metal oxide ingredients or constituents can be derived by precipitation as hydrous metal oxides or hydroxides from an aqueous soluexamples relative to the preparation of'supported" chromium oxide catalysts, which constitute preferred species and which are regarded herein as best exemplifying the invention.

In one method of practicing the invention, a concentrated solution comprising trivalent chrmium compounds is prepared in any convenient manner, for example, by melting or dissolving a salt, such as chromic acetate, chromic chloride, chromic nitrate, or the like, in its own water of crystallization or in a minimum quantity of water. A porous carrier material, such as activated aluminum oxide, bauxite or silica gel, having granules of the desired size and shape, is impregnated with the solution and excess water may be removed by filtration and/or evaporation. The support or carrier may, in general, be any granular porous material that is capable of withstanding elevated temperatures (up to about 700 C. or higher) and that is resistant to conditions which will prevail during revivification of the catalyst by an oxygen-containing gas at an elevated temperature or other influences which will be encountered in. use. Particularly desirable carriers are minerals capable of withstanding dehydrogenation temperatures without mechanical failure and which possess not only high specific surface and porosity but also ready perviousness. Supports which have these characteristics are such as are obtained from hydrous minerals, especially hydrous crystalline minerals, such as gibbsite and gypsum, by heating them to drive out combined water, so that a pervious skeletal structure remains. Certain metamorphosed mineral, such as mica and its relatives and various clays having a somewhat stratified structure, such as bentonite and montmorillonite, may be used as supports; those having good porosity and perviousness may be readily selected by simple tests for these characteristics. Among suitable preferred carriers are alumina, bauxite, k-ieselguhr, magnesia, silica gel, thoria, and. zirconia; These supports are not to be considered as being complete equivalents of each other: they may or may not possess catalytic activity of their 'own. Of these materials, alumina and bauxite are usually preferred, mainly because they are readily available in large quantities at low cost and are of substantially uniform quality. The carrier, in the form of granules of any desired size and shape, is preferably heated before use to a temperature of about 600 C.', in order to expel volatile matter pecially desirable since they possess less tendency to produce packing and channeling in use.

impregnation of the carrier with the solution may be effected in various conventional ways. A simple method consists in pouring the solution over the carrier, stirring the mass, and removing excess liquid by any convenient means, such as by decantation, filtration, or evaporation. In

' nate heating and cooling may be used to effect incorporation of the catalytic material into the support. The impregnated granules may be partially or wholly dried and reimpregnated and coated as many times as desired, to increase the quantity of catalytic material incorporated with the carrier. -Normally, however, one impregnation is sufficient if the subsequent procedure as detailed herein is followed.

The carrier granules may be of any desired size and shape. Granular particles within the, range of 4 to 40 mesh are preferred. The size of the particles may be outside this preferred range, but

if it is much smaller than 40 mesh, the mixture is preferably pelleted or briquetted or otherwise formed into composite granules, each consisting of several carrier granules impregnated with the catalytic component. Such composite granules may be obtained, for example, by separating the mixture of carrier granules and catalytic material from excess liquid, as by filtering, expressing the liquid by pressure, or the like, and breaking up the resulting cake into composite granules of suitable size. Other conventional methods for obtaining composite granules 0r pellets of the desired size may be used, however.

The proportion of active metal oxides to carrier in the catalystmay be yaried widely. An active metal oxide content of ;-from approximately 5 to approximately 50 per cent by weight of the final composite catalyst is generally preferred, but proportions outside of this range may be used if desired. For dehydrogenation catalysts the active metal oxide component usually consists of one or more oxides ofone or more metals of the 3rd, 4th, 5th, and 6th groups of the periodic table. Oxides of metals of the 6th group are preferred, however, especially oxides of chromium, which are exceptionally active. If desired, several metal oxides may be used in combination; for example, one or more relatively less active, infusible, difiicultly reducible oxides may be incorporated in the catalyst to stabilize it against thermal shock or to modify its action. For such purposes, alumina, zirconia, titania, thoria, silica, boric oxide, and magnesia are suitable. Such modifying or stabilizing materials may be introduced by incorporation of the corresponding salts in the original chromium-containing solution prior to impregnation of the carrier therewith.

drying step may be omitted.

vention will depend upon'the contemplated use of Y the resulting catalyst.

After impregnation of the carrier with the solution and removal of excess liquid therefrom, the resulting impregnated granules may be dried to the point of being visually dry. They may be partially dried, for example, in air at a temperature in the range of approximately 40 to 100 C. for a period of from approximately one hour to two or more days dependent upon the temperature. This drying step is not essential, its chief function being to facilitate handling of the material. However, if too much water iszleft in the material some oozing out or creeping of hydrous oxides and disruption of the carrier granules may occur in the final treatment with anhydrous ammonia. Since water dissolves in anhydrous ammonia, it is desirable to remove as much excess water as possible from the impregnated carrier so as to simplify the subsequent recovery of ammonia in the process. In some instances, for example when the carrier is very porous or absorptive and the proportion of metal oxide is relatively small, the

j The impregnated support is thensubjected to the action of substantially anhydrous ammonia.

The granules may be immersed in liquid ammonia for a time suflicient to complete the reaction of ammonia with the salts in the catalyst. Preferably, however, because of the comparative difficulty and the refrigeration required in handling liquid ammonia, gaseous ammonia is used. Gaseous substantially. anhydrous ammonia, which may be diluted, if desired, with other inert gases, such as methane or .nitrogen, is passed over the granules at a temperature which preferably is alyst, before or after ammonia treatment, with below approximately 100 C., that is, below a temperature at which all water is driven off. A temperature much above 100 C. at the start of the ammonia treatment tends to make the catalytic metal oxides relatively less adherent to the support, apparently because of too rapiddehydration. After the ammonia treatment is 'partly completed, the temperature may, if desired, be raised somewhat above 100 C. The time of ammonia treatment has been found not to be critical and need only be long enough, such as 1- to 15 minutes or more, dependent upon the velocity and dilution of the ammonia, to complete the reaction between ammonia and the metal salts. Some water is usually expelled because of heat evolved in the treatment. The progress of the reaction with gaseous ammonia may be followed advantageously by checking the temperature of the catalyst; the reaction is judged complete, and the flow of ammonia gas may be stopped, when the temperature in the catalyst drops again to the temperature of the surrounding atmosphere.

Too much ammonia must be avoided in cases of metal compounds whichform soluble complexes with excess ammonia." v i The resulting ammonia-treated catalyst material is dehydrated as by heating gradually from roomtemperature up to approximately 450 C.

dilute aqueous alkaline solutions, such assolutions of soluble alkali-metal or alkallne-earthalkaline compound used for neutralizing the acid 1 residue should be one which forms stable, relatively nonvolatile salts with acids, so that no volatilization of catalyst constituents occurs at the temperatures of use of the catalyst. The alkaline solutions used for this treatment are preferably dilute solutions which contain from approximately 0.1 to approximately 10.0 per cent by weight of the alkaline compound, and preferably such as contain from approximately 0.5 to approximately 5 per cent. The optimum concentration and amount of alkaline solution for use in a particular case may be readily determined by trial. Among alkaiizing materials which may be used in this way are: sodium hydroxide, potassium hydroxide, rubidium hy-.

A hot concentrated aqueous solution containing 400 grams of chromium nitrate (Cr (N03) 3.91120) is poured over 1000 grams of activated aluminum oxide pellets in an evacuated container, and the mixture is stirred until all or nearly all the solui tion is absorbed or deposited in and on. the pel-' lets. The resulting pellets are partially dried in air at a temperature of approximately to C. for 6 hours. and are then placed in a glass tube. Substantially anhydrous gaseous ammonia is passed through the tube for about three hours.

Heat is liberated during the first part of the onehour period, and some moisture condenses at the exit end of the glass tube.

This catalyst is used for dehydrogenating normal butane to butylenes as follows: It is placed in a catalyst chamber of a continous dehydrogenation system and is heated slowly from room temperature to 550 C. in a stream of hydrogen.

At 550 C., the flow of hydrogen is cut off, and a stream of normal butane is charged into the catalyst chamber at a space velocity of 1000 gaseous volumes per volume of catalyst per hour. The initial conversion per pass of normal butane to butylenesis approximately 30 mol per cent; this conversion is maintained by gradual raising of the temperature to compensate for decreasing activity Of the catalyst, until at the end of 3 hours the temperature is 620 C. The catalyst is then reactivated by passing a stream of air over it for one hour; during this time the maximum temperature reached is .700" C. The reactivated catalyst is reduced by passing a stream of hydrogen through it at 550 C., and the flow of normal butane is started again. The catalyst is used in this way for 10 cycles and shows no apparent permanent decrease in activity.

Errample If A catalyst prepared as described in Example I is used as follows: It is gradually heated from The period of treating at 520 C. The reduced catalyst is usedior a second cycle in which it gives results that'are substantially identical with those obtained in the first cycle, that is, it is used for hours at a constant conversion or 18 per cent between the temperatures of 520 and 600 C.

Example III A hot concentrated aqueous solution containing 400 grams of chromium. nitrate (Cl'(NOa)a'9H:O) and 112 grams 01' aluminum nitrate.

is poured onto 1000 grams or activated aluminum oxide pellets. The mixture is placed under a pressure of 2 to 8 atmospheres of nitrogen and is allowed to stand for 12 hours. The excess liquid is then removed by decantation. The impregnated pellets are then placed in a glass tube, and substantially anhydrous gaseous ammonia, diluted with!) parts by volume of nitrogen, is slowly passed over them for hours. The heat liberated is not as evident as in Example I. At the end of the treating period; the catalyst-containing pellets are removed from the tube. The catalyst is used for dehydrogenation as described in Example I, and substantially the same results are obtained.

Example IV A heated aqueous solution containing 400 grams of chromium nitrate (Cr(NO:)a-9H:O) 33 grams of zirconyl nitrate -(Z1'O(NOa)a-2H2O) and 48 grams of magnesium nitrate (lidg(NOa)a-6Ha0) is poured over 100 grams of activated aluminum oxide pellets in an evacuated container. The mixture is stirred for one hour, and the excess water is then removed by filtration. The partly dried impregnated pellets are then placed in an evacuated pressure vessel and anhydrous liquid ammonia is added slowly under pressure until the pellets are completely covered. The mixture is allowed to stand for approximately one hour; the pressure is then released and ammonia is allowed to evaporate, after which the pelletsare removed from the vessel. The pellets are round to have substantiallythe size and shape or the original unimpregnated carrier material. when used to dehydrogenate normal butane, the same procedure is used, and substantially the same results are obtained, as in Example I.

In the foregoing examples, the utilization of catalysts prepared'according to the process of this invention has been confined to the dehydrogenation of butane for the sake of making direct comparisons of catalyst behavior. However,

, many catalysts prepared according to the process of the invention are equally applicable to dehydrogenation of other paraflln hydrocarbons, from ethane through the waxes, to form the corresponding olefins; to dehydrogenation of olefins to the-corresponding diolefins; and to other reactions known to be promoted by the type of catalyst concerned.

From the foregoing description and examples, it will be apparent to those skilled in the art 01' preparingcatalysts, that the use of anhydrous assasis ammonia as a precipitating agent to prepare an active supported metal oxide catalyst from a supporting material impregnated with a metal salt is a distinct advance over iormer methods,

which are characterized by the use 01' an aqueous alkaline or ammonia solution as the iinal precipitating agent.

Although the processes described hereinabove are directed to the production of catalysts comprising one or more metal oxides, it is obvious that one or more particular metal oxide components oi said catalysts can be reduced, and in many hydrocarbon conversion reactions may actually be so reduced, to the corresponding metals. Thus the invention is directed to the production ofsupported catalysts in which the supported catalytic material comprises initially a metal oxide which may be converted subsequently, wholly or partially, toa metal.

There are many modifications of my invention that will be obvious to those skilled in the art of catalysis and catalyst preparation. -For example, although for the sake of clarity and simplicity the foregoing description has dealt mainly with dehydrogenation-type catalysts which comprises chromium oxide, the invention is applicable generally to supported catalysts in which one or more 01 the active ingredients are metal oxides derivable from solutions by precipitation or reaction with ammonia and is applicable to reactions other than dehydrogenation, such as aromatization, isomerization, desuliurization, etc.,

40 bons.

that are well-known in the art of treating and/or converting hydrocarbons or other organic compounds. Some 01 these reactions such as hydrogenation, dehydrogenation, dehydrocyclization, and the like, when applied to hydrocarbons, may be grouped together under the term of changing the carbonhydrogen ratio or hydrocar- Hence, the invention should not be restricted except as specified in the appended claims.

I claim:

1. In the process of preparing a catalyst comprising a metal oxide supported on a granular, porous and highly adsorptive catalyst carrier material of the desired size and shape which comprises impregnating the porous catalyst carrier material with a concentrated aqueous medium comprising a compound of a metal that is capable of yielding byreaction with alkalis a catalytically active metal oxide and thereafter precipitating the catalytically active metal oxide on the impregnated carrier material-with an alkali, the improvement whereby the metal oxide is precipitated upon the carrier material without substantial disruption of the catalyst carrier material and without the formation of a substantial amount of fine, which comprises impregnating the catalyst carrier material with the concentrated aqueous medium comprising the metal compound in a relatively small proportion insufllcient to cause disruption of the' carrier on treatment with ammonia, removing excess liquid therefrom, subjecting the resulting material to the action of substantially anhydrous ammonia to eiIect precipitation of the metal oxide throughout the carriermaterial, and heating the resulting material to remove water and ammonium compound therefrom.

2. In the process of preparing a catalyst comprising a metal oxide supported on a porous catalyst carrier material which comprises impregnating the porous catalyst carrier material with a concentrated aqueous medium comprising a compound of ametal that is capable of yielding by'reaction with alkalies a catalytically active metal oxide and thereafter precipitating the catalytlcally active metal oxide on the impregnatedcarrier material with an alkali, the improvement whereby the metal oxide is precipitated upon the carrier material without substantial disruption ofthe catalyst carrier material and without the formation of a substantial amount of fines, which comprises impregnating the catalyst carrier material with the concentrated aqueous medium comprising the metal compound, removing a substantial portion of the excess liquid therefrom, partially but incompletely drying said impregnated catalyst carrier material at a temperature below approximately 100 C., and subsequently subjecting the resulting material to the action of substantially anhydrous ammonia to effect precipitation of the metal oxide upon the carrier material and thereafter heating the resulting material to remove water and ammonium compounds therefrom.

3. The process as defined in claim 2, in which said metal compound is a salt of a p'olyvalent the resulting ammonia-treated catalytic materialis subsequently treated with an alkalizin'g solution comprising a substantially nonvolatile alkaline compound that forms substantially nonvolatile. salts with acids, in an amount at least suflicient tocombine with any residual acidic decomposition products formed in said ammonia treatment.

9. In the process of preparing a, catalyst comprising a metal oxide supported on a porous catalyst carrier material which comprises impregnating the porous catalyst carrier material with an aqueous solution of a compound of a metal selected from groups 3 to 6, inclusive, of the periodic table that is capable of yielding by reaction with alkalies a catalytically active metal oxide and thereafter precipitating the 'catalytically active metal oxide on the impregnated carrier material I with an alkali, the improvement whereby the metal oxide is precipitated upon the carrier material without substantial disruption of the catalyst carrier material and without the formation of a substantial amount of fines, which comprises impregnating the catalyst carrier material with the solution comprising the said metal compound, removing a substantial portion of the excess liquid therefrom, partially but incompletely drying said impregnated catalyst carrier material at'a temperature below approximately 100 0., and

subsequently passing substantially anhydrous ammonia overthe partially dried impregnated material to effect precipitation of the metal oxide upon the carrier material and thereafter heating the resulting material to remove water and ammonium compounds therefrom;

10. A processof preparing a catalyst comprising chromium oxide supported on a porous granular catalyst carrier material which comprises impregnating the porous granular catalyst carrier with an aqueous solution of a chromium compound, and thereafter removing a substantial portion of the excess'liquid therefrom, partially but incompletely drying said impregnated catalyst carrier. material at a temperature within the range of approximately 40 to approximately 100 0., and subsequently passing substantially anhydrous ammonia over the partially dried impregnated catalyst carrier at a temperature below approximately 100 C. to effect precipitation of chromium oxide on the carrier material.

11. A process of preparing a catalyst comprising chromium oxide supported on a porous granular catalyst carrier material which comprises impregnating the porous granular catalyst carrier material with an aqueous solution of a chromium salt of a monobasic acid and thereafter removin a substantial portion of the excess liquid therefrom, partially but incompletely drying said impregnated catalyst carrier at a temperature within the range of approximately 40 to approximately 100 C., and'subsequently passing substantially anhydrous ammonia over the partially dried impregnated catalyst carrier at a temperature below approximately 100 C. to effect precipitation of chromium oxide on the carrier material.

12. A process of preparing a catalyst comprising chromium oxide and aluminum oxide supported on a porousgranular aluminum oxide carrier material, which comprises impregnating the porous granular catalyst material with an aqueous solution of a mixture of water-soluble chromium and aluminum salts of monobasic acids and thereafter removing a substantial portion of the excess liquid therefrom, partially but incompletely drying said impregnated catalyst car.- rier at a temperature within the range of approximately to approximately 100 C., and

subsequently passing substantially anhydrous ammonia over the partially dried impregnated catalyst carrier at a temperature below approximately 100 C. to effect precipitation of chromium and aluminum oxides on the carrier material.

13. A supported metal oxide catalyst comprising a metal oxide supported on and uniformly distributed throughout a porous catalyst carrier material in particulate form and free from substantial amounts of fines prepared by impregnating a porous catalyst carrier material with a concentrated aqueous medium comprising a compound of a metal that is capable of yielding by reaction with alkalies a catalytically active metal oxide, removing a substantial portion of the excess liquid therefrom, partially but'incompletely drying said impregnated catalyst carrier material at a temperature below approximately C. and subsequently subjecting the resulting material to theaction of substantially anhydrous ammonia to precipitate the metal oxide upon the carrier material and thereafter heating the resulting material to remove water and ammonium compounds therefrom said catalyst having granules of substantially uniform size and shape corresponding to the dimensions of the particulate carrier prior to precipitation of the metal oxide within the pores thereof.

143A supported metal oxide catalyst comprising a metal oxide supported on and uniformly distributed throughout a porous catalyst carrier material in particulate form and free from substantial amounts of fines prepared by impregnatcapable of yielding byreaction with alkalies a l catalytically active metal oxide, removing a.substantial portion or the excess liquid therefrom, partially but incompletely drying said impreghated catalyst carrier material at a temperature below approximately 100 Cl, and subsequently passing substantially anhydrous ammonia over the partially dried impregnated material to eriect precipitation of the metal oxide upon the carrier material and thereafter heating the re-' sulting material to remove water and ammonium substantial amounts of tines prepared by impreghating a porous catalyst carrier material with an aqueous solution of a water-soluble chromium salt or a monobasic acid, removinga substantial portion of the excess liquid thereirom. partially butincompletely drylngfsaid impregnated catalyst carrier. at a temperature within the range oi approximately 40 to approximately-100' -C., and subsequently passing substantially anhydrous'ammonia over the partially dried impregnated catalyst carrier at a temperature below approximately 100 C. to eflect precipitation oi chromium oxide on the carrier material said catalyst having granules of substantially uniform size and shape corresponding to the dimensions oi the particulate carrier prior to precipitation of the metal oxide within the pores thereoi.

JOHN D. UPI-LAM. 

